Methods of pest control in soybean

ABSTRACT

Methods of controlling pests on soybean plants, comprising: applying to a crop of soybean plants, the locus thereof, or propagation material thereof, a compound of formula (Ia),wherein X1, R1, R4, R5, *, and **, as defined in claim 1, wherein the soybean plants are Bt plants.

This application is a continuation of U.S. Application Ser. No.14/419,074, filed Feb. 2, 2015, which is a national stage under §371 ofInternational Patent Application PCT/EP2013/065785, filed Jul. 26, 2013,which claims priority to EP 12195021.6, filed Nov. 30, 2012, andEP12179260.0, filed Aug. 3, 2012, the entire contents of each areincorporated by reference herein.

The present invention relates to methods of pest control in soybeancrops.

Stink bugs (Hemiptera Pentatomidae) are true bugs which can besignificant pests when present in large numbers. The nymphs and adultshave piercing mouthparts which most use to suck sap from plants.According to Stewart et al., Soybean Insects - Stink bugs, University ofTennessee Institute of Agriculture, W200 09-0098, stink bugs areprobably the most common pest problem in soybean. Although they may feedon many parts of the plant, they typically target developing seedincluding the pods, meaning that injury to soybean seed is the primaryproblem associated with stink bug infestations.

Of the complex of sucking bugs that occur in cultivation, the brownstinkbug Euschistus heros is currently considered to be the mostabundant species in northern Paraná to Central Brazil (Corrêa-Ferreira &Panizzi, 1999), and is a significant problem in soybean (Schmidt et al.,2003). The bugs occur in soybeans from the vegetative stage and areharmful from the beginning of pod formation until grain maturity. Theycause damage to the seed (Galileo & Heinrichs 1978a, Panizzi & SlanskyJr., 1985) and can also open the way to fungal diseases and causephysiological disorders, such as soybean leaf retention (Galileo &Heinrichs 1978, Todd & Herzog, 1980).

Control of stinkbugs in soybean is often vital to prevent significanteconomic damage. Insecticides commonly used to control stinkbugs includepyrethroids, neonicotinoids and organophosphates, although pyrethroidinsecticides are usually the method of choice for controlling stink bugsin soybean. However, there are increasing problems with insecticideresistance, particularly in brown stink bug populations and particularlyto pyrethroids. Euschistus heros can also be difficult to manage usingorganophosphates or endosulfan (Sosa-Gomez et al., 2009). There istherefore a need for effective alternative methods of controllingstinkbugs in soybean.

Compounds that are insecticidally, acaricidally, nematicidally and/ormoluscicidally active by antagnonism of the gamma-aminobutyric acid(GABA)-gated chloride channel, and which comprise a partially saturatedheterocycle that is substituted by a haloalkyl substituent and one ortwo optionally substituted aromatic or heteroaromatic rings, represent anew class of pesticides that are described for example in Ozoe et al.Biochemical and Biophysical Research Communications, 391 (2010) 744-749.Compounds from this class are broadly described in WO 2005/085216(EP1731512), WO 2007/123853, WO 2007/075459, WO 2009/002809, WO2008/019760, WO 2008/122375, WO 2008/128711, WO 2009/097992, WO2010/072781, WO 2010/072781, WO 2008/126665, WO 2007/125984, WO2008/130651, JP 2008110971, JP 2008133273, JP 2009108046, WO2009/022746, WO 2009/022746, WO 2010/032437, WO 2009/080250, WO2010/020521, WO 2010/025998, WO 2010/020522, WO 2010/084067, WO2010/086225, WO 2010/149506, WO 2010/108733 andWO 2011/067272.

It has now surprisingly been found that particular insecticides fromthis new class of gamma-aminobutyric acid (GABA)-gated chloride channelantagonists (disclosed in e.g. WO 2011/067272) are highly effective atcontrolling stinkbugs, and may in some cases provide greater controlthan the current market standard. It has also surprisingly been foundthat some compounds exhibit significantly higher activity againststinkbugs than structurally similar compounds. These compounds thereforerepresent an important new solution for safeguarding soybean crops fromstinkbugs, particularly where stink bugs are resistant to currentmethods.

In a first aspect the invention provides a method comprising applying toa crop of soybean plants, the locus thereof, or propagation materialthereof, a compound of formula I

wherein

-   -B¹-B²-B³- is —C═N—O—, —C═N—CH₂—, —C═CH₂—O— or —N—CH₂—CH₂—;

-   L is a direct bond or methylene;

-   A¹ and A² are C—H, or one of A¹ and A² is C—H and the other is N;

-   X¹ is group X

-   

-   R¹ is C₁-C₄alkyl, C₁-C₄haloalkyl or C₃-C₆cycloalkyl;

-   R² is chlorodifluoromethyl or trifluoromethyl;

-   each R³ is independently bromo, chloro, fluoro or trifluoromethyl;

-   R⁴ is hydrogen, halogen, methyl, halomethyl or cyano;

-   R⁵ is hydrogen;

-   or R⁴ and R⁵ together form a bridging 1,3-butadiene group;

-   p is 2 or 3.

In a further aspect the invention provides a method of controllingand/or preventing infestation of stinkbugs in soybean comprisingapplying to a crop of soybean plants, the locus thereof, or propagationmaterial thereof, a compound of formula I. The stinkbugs may be thosethat are resistant to one or more other insecticides.

In a further aspect the invention provides a method of controllingand/or preventing infestation of stinkbugs in a crop of useful plantscomprising applying to a crop of useful plants, the locus thereof, orpropagation material thereof, a compound of formula I. The stinkbugs maybe those that are resistant to one or more other insecticides.

In a further aspect the invention provides use of a compound of formulaI for control of stinkbugs in a crop of useful plants. The use may befor controlling stinkbugs that are resistant to one or more otherinsecticides.

In a further aspect the invention provides a method of controllingand/or preventing infestation of insects from the genus Euschistus in acrop of useful plants comprising applying to a crop of useful plants,the locus thereof, or propagation material thereof, a compound offormula I. The insects from the genus Euschistus may be those that areresistant to one or more other insecticides.

In a further aspect the invention provides use of a compound of formulaI for control of insects from the genus Euschistus in a crop of usefulplants. The use may be for controlling insects from the genus Euschistusthat are resistant to one or more other insecticides.

In a further aspect the invention provides a method of controllingand/or preventing infestation of insects from the genus Euschistus in acrop of soybean plants comprising applying to a crop of soybean, thelocus thereof, or propagation material thereof, a compound of formula I.The insects from the genus Euschistus may be those that are resistant toone or more other insecticides.

In a further aspect the invention provides use of a compound of formulaI for control of insects from the genus Euschistus in a crop of soybeanplants. The use may be for controlling insects from the genus Euschistusthat are resistant to one or more other insecticides.

In a further aspect the invention provides a method of controllingand/or preventing infestation of Euschistus heros in a crop of usefulplants comprising applying to a crop of useful plants, the locusthereof, or propagation material thereof, a compound of formula I. TheEuschistus heros may be resistant to one or more other insecticides.

In a further aspect the invention provides use of a compound of formulaI for control of Euschistus heros in a crop of useful plants. The usemay be for controlling Euschistus heros that is resistant to one or moreother insecticides.

In a further aspect the invention provides a method of controllingand/or preventing infestation of Euschistus heros in a crop of soybeanplants comprising applying to a crop of soybean, the locus thereof, orpropagation material thereof, a compound of formula I. The Euschistusheros may be resistant to one or more other insecticides.

In a further aspect the invention provides use of a compound of formulaI for control of Euschistus heros in a crop of soybean plants. The usemay be for controlling insects Euschistus heros that are is resistant toone or more other insecticides.

Stinkbugs that are resistant to one or more other insecticides arepreferably resistant to pyrethroid, neonicotinoids and/ororganophosphates, more preferably pyrethroid insecticides.

In a further aspect the invention provides a method for obtainingregulatory approval for the use of one or more of a compound of formulaI to control stinkbugs, in particular the genus Euschistus and inparticular the species Euschistus heros, and in particular in soybeanplants, comprising at least one step of referring to, submitting orrelying on biological data showing that said active ingredient reducesinsect pressure.

The compounds of formula (I) may exist in different geometric or opticalisomers or tautomeric forms. This invention covers all such isomers andtautomers and mixtures thereof in all proportions as well as isotopicforms such as deuterated compounds. The invention also covers salts andN-oxides of the compounds of the invention.

Alkyl groups (either alone or as part of a larger group, such asalkoxy-, alkylthio-, alkylsulfinyl-, alkylsulfonyl-, alkylcarbonyl- oralkoxycarbonyl-) can be in the form of a straight or branched chain andare, for example, methyl, ethyl, propyl, prop-2-yl, butyl, but-2-yl,2-methyl-prop-1-yl or 2-methyl-prop-2-yl. The alkyl groups arepreferably C₁-C₆, more preferably C₁-C₄, most preferably C₁-C₃ alkylgroups. Where an alkyl moiety is said to be substituted, the alkylmoiety is preferably substituted by one to four substituents, mostpreferably by one to three substituents.

Halogen is fluorine, chlorine, bromine or iodine.

Haloalkyl groups are alkyl groups which are substituted by one or moreof the same or different halogen atoms and are, for example,difluoromethyl, trifluoromethyl, chlorodifluoromethyl or2,2,2-trifluoro-ethyl.

Preferred substituent definitions are described below and may becombined in any combination, including with original definitions.

-B¹-B²-B³- is preferably —C═N—O—.

A¹ and A² are preferably C—H.

Preferably X¹ is 3,5-dichlorophenyl-, 3-chloro-4-fluorophenyl-,3-fluoro-4-chlorophenyl-, 3,4-dichlorophenyl-, 3-chloro-4-bromophenyl-,3,5-dichloro-4-fluorophenyl-, 3,4,5-trichlorophenyl-,3,4,5-trifluorophenyl-, 3-chloro-5-bromophenyl-,3-chloro-5-fluorophenyl-, 3-chloro-5-(trifluoromethyl)phenyl-,3,4-dichloro-5-(trifluoromethyl)phenyl-,3,5-bis(trifluoromethyl)phenyl-,4-chloro-3,5-bis(trifluoromethyl)phenyl-, 3-(trifluoromethyl)phenyl-,more preferably 3-chloro-5-bromophenyl-,3-chloro-5-(trifluoromethyl)phenyl-, 3,5-dichloro-4-fluorophenyl-,3,4,5-trichlorophenyl-, 3,5-bis(trifluoromethyl)phenyl-,3-(trifluoromethyl)phenyl-, 3,5-dichloro-4-bromophenyl-,3-bromo-5-(trifluoromethyl)phenyl-, 3,5-dibromophenyl-, or3,4-dichlorophenyl-, even more preferably 3,5-dichloro-phenyl,3,5-dichloro-4-fluorophenyl-, 3,4,5-trichlorophenyl-,3,5-bis(trifluoromethyl)phenyl, most preferably R⁴ is3,5-dichloro-phenyl.

R¹ is preferably methyl, ethyl, propyl, butyl, cyclopropyl, cyclobutyl,trifluoroethyl, difluoroethyl. Ethyl and trifluoroethyl are particularlypreferred.

R² is preferably trifluoromethyl.

Preferably each R³ is independently chlorine or fluorine, mostpreferably chlorine.

R⁴ is preferably chloro or methyl, most preferably methyl.

R⁵ is preferably hydrogen.

L is preferably a direct bond.

In one group of compounds -B¹-B²-B³- is —C═N—O—.

In one group of compounds -B¹-B²-B³- is —C═N—CH₂—.

In one group of compounds -B¹-B²-B³- is —C═CH2—O—.

In one group of compounds -B¹-B²-B3- is —N—CH₂—CH2—.

In one embodiment A¹ and A² are C—H, R² is trifluoromethyl, and R⁵ ishydrogen.

In one embodiment A¹ and A² are C-H, R² is trifluoromethyl, R⁵ ishydrogen and L is a direct bond.

In one embodiment -B¹-B²-B³- is —C═N—O—, A¹ and A² are C—H, R² istrifluoromethyl, R⁵ is hydrogen and L is a direct bond.

In one embodiment -B¹-B²-B³- is —C═N—O—, A¹ and A² are C-H, R² istrifluoromethyl, R⁴ is halogen or methyl, R⁵ is hydrogen and L is adirect bond.

In one embodiment -B¹-B²-B³- is —C═N—O—, A¹ and A² are C—H, R² istrifluoromethyl, R3 is chloro or fluoro, R⁴ is halogen or methyl, R⁵ ishydrogen and L is a direct bond.

In one embodiment A¹ and A² are C—H, R² is trifluoromethyl, R⁴ ismethyl, R⁵ is hydrogen, each R³ is chlorine, p is 2.

In one embodiment R¹ is C₁-C₄alkyl, e.g. methyl, ethyl or propyl, e.g.methyl or ethyl, e.g. ethyl.

In one embodiment X¹ is group Xa

In one embodiment R¹ is C₁-C₈alkyl, e.g. methyl, ethyl or propyl, e.g.methyl or ethyl, e.g. ethyl and X¹ is group Xa.

In one embodiment R¹ is methyl.

In one embodiment R¹ is ethyl.

In one embodiment R¹ is 2,2,2-trifluoroethyl.

In one embodiment R¹ is 2,2-difluoroethyl.

In one embodiment X¹ is 3,5-dichlorophenyl.

In one embodiment X¹ is 3,5-dichloro-4-fluorophenyl.

In one embodiment X¹ is 3,4,5-trichlorophenyl.

In one embodiment R¹ is methyl and X¹ is 3,5-dichlorophenyl.

In one embodiment R¹ is methyl and X¹ is 3,5-dichloro-4-fluorophenyl.

In one embodiment R¹ is methyl and X¹ is 3,4,5-trichlorophenyl.

In one embodiment R¹ is ethyl and X¹ is 3,5-dichlorophenyl.

In one embodiment R¹ is ethyl and X¹ is 3,5-dichloro-4-fluorophenyl.

In one embodiment R¹ is ethyl and X¹ is 3,4,5-trichlorophenyl.

In one embodiment R¹ is 2,2,2-trifluoroethyl and X¹ is3,5-dichlorophenyl.

In one embodiment R¹ is 2,2,2-trifluoroethyl and X¹ is3,5-dichloro-4-fluorophenyl.

In one embodiment R¹ is 2,2,2-trifluoroethyl and X¹ is3,4,5-trichlorophenyl.

In one embodiment R¹ is 2,2-difluoroethyl and X¹ is 3,5-dichlorophenyl.

In one embodiment R¹ is 2,2-difluoroethyl and X¹ is3,5-dichloro-4-fluorophenyl.

In one embodiment R¹ is 2,2-difluoroethyl and X¹ is3,4,5-trichlorophenyl.

Compounds of formula I may exist as compounds of formula I* or compoundsof formula I**.

Compounds of formula I** are more biologically active than compounds offormula I*. Compounds of formula I may be a mixture of compounds I* andI** in any ratio e.g. in a molar ratio of 1:99 to 99:1, e.g. 10:1 to1:10, e.g. a substantially 50:50 molar ratio. Preferably the compound offormula I is a racemic mixture of the compounds of formula I** and I* oris enantiomerically enriched for the compound of formula I**. Forexample, when the compound of formula I is an enantiomerically enrichedmixture of formula I**, the molar proportion of compound I** compared tothe total amount of both enantiomers is for example greater than 50%,e.g. at least 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, or atleast 99%. In a preferred embodiment the compound of formula I is acompound of formula I** in substantially pure form, e.g. it is providedsubstantially in the absence of the alternative enantiomer.

Compounds of formula I may also exist as compounds of formula I′ orcompounds of formula I″.

(S = S stereochemistry, R = R stereochemistry)

Compounds of formula I″ are often more biologically active thancompounds of formula I′. The compound of formula I may be a mixture ofcompounds I′ and I″ in any ratio e.g. in a molar ratio of 1:99 to 99:1,e.g. 10:1 to 1:10, e.g. a substantially 50:50 molar ratio. Preferablythe compound of formula I is a racemic mixture of the compounds offormula I″ and I′ or is enantiomerically enriched for the compound offormula I″. For example, when the compound of formula I is anenantiomerically enriched mixture of formula I″, the molar proportion ofcompound I″ compared to the total amount of both enantiomers is forexample greater than 50%, e.g. at least 55, 60, 65, 70, 75, 80, 85, 90,95, 96, 97, 98, or at least 99%. In one embodiment the compound offormula I is a compound of formula I″ in substantially pure form, e.g.it is provided substantially in the absence of the alternativeenantiomer.

The above stereocentres give rise to four stereoisomers:

In one embodiment the compound of formula I is a mixture comprisingcompounds I-i, I-ii, I-iii and I-iv, wherein the mixture is enriched forthe compound of formula I-iv, e.g. the molar proportion of compound I-ivcompared to the total amount of the four isomers is for example greaterthan 25%, e.g. at least 30, 35, 40, 50, 55, 60, 65, 70, 75, 80, 85, 90,95, 96, 97, 98, or at least 99%.

In another embodiment the compound of formula I is a mixture comprisingcompounds I-i, I-ii, I-iii and I-iv, wherein the molar amount of thecompound of formuila I-iv is greater than the molar amount of thecompound of formula I-i, and the molar amount of the compound I-ii, andthe molar amount of the compound of formula I-iii, in other words, thecompound of formula I-iv is the most abundant isomer in the mixture. Forexample the molar amount of compound of formula I-iv is at least 1, 2,5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 56, 70, 75, 80, 85, 90,or even at least 95% greater than the combined amount of the compound offormula I-iv and I-i, the combined amount of the compound of formulaI-iv and I-ii, and the combined amount of the compound of formula I-ivand I-iii.

Although B¹-B²-B³ is shown above as C═N—O, the same applies in respectof the stereoisomers when B¹-B²-B³ is —C═N—CH2—, —C═CH₂—O— and—N—CH₂—CH₂—.

In one embodiment the compound of formula I-iv is the most abundantisomer and R¹ is C₁-C₄alkyl, e.g. methyl, ethyl or propyl, e.g. methylor ethyl, e.g. ethyl.

In one embodiment the compound of formula I-iv is the most abundantisomer and R¹ is C₁-C₄alkyl, e.g. methyl, ethyl or propyl, e.g. methylor ethyl, e.g. ethyl and X¹ is group Xa.

In one embodiment the compound of formula I-iv is the most abundantisomer and R¹ is methyl.

In one embodiment the compound of formula I-iv is the most abundantisomer and R¹ is ethyl.

In one embodiment the compound of formula I-iv is the most abundantisomer and R¹ is 2,2,2-trifluoroethyl.

In one embodiment the compound of formula I-iv is the most abundantisomer and R¹ is 2,2-difluoroethyl.

Preferred compounds of formula I are shown in the Tables below.

TABLE A Compounds of formula (I-a)

(I-a) Table A provides 78 compounds and mixtures of formula (I-a)wherein R¹ has the values listed in table X below. The symbols ^(∗) and^(∗∗) indicate the location of the chiral centres.

TABLE B Compounds of formula (I-b)

(I-b) Table B provides 78 compounds and mixtures of formula (I-b)wherein R¹ has the values listed in table X below. The symbols ^(∗) and^(∗∗) indicate the location of the chiral centres.

TABLE C Compounds of formula (I-c)

(I-c) Table C provides 78 compounds and mixtures of formula (I-c)wherein R¹ has the values listed in table X below. The symbols ^(∗) and^(∗∗) indicate the location of the chiral centres.

TABLE D Compounds of formula (I-d)

(I-d) Table D provides 78 compounds and mixtures of formula (I-d)wherein R¹ has the values listed in table X below. The symbols ^(∗) and^(∗∗) indicate the location of the chiral centres.

TABLE E Compounds of formula (I-e)

(I-e) Table E provides 78 compounds and mixtures of formula (I-e)wherein R¹ has the values listed in table X below. The symbols ^(∗) and^(∗∗) indicate the location of the chiral centres.

TABLE F Compounds of formula (I-f)

(I-f) Table F provides 78 compounds and mixtures of formula (I-f)wherein R¹ has the values listed in table X below. The symbols ^(∗) and^(∗∗) indicate the location of the chiral centres.

Table X represents Table A when X is A, Table B when X is B, Table Cwhen X is C, Table D when X is D, Table E when X is E, Table F when X isF.

Compound numbers Stereochemistry at ^(∗) Stereochemistry at ^(∗∗) R¹ X.1Racemic mixture Racemic mixture ethyl- X.2 Racemic mixture Racemicmixture butyl- X.3 Racemic mixture Racemic mixture but-2-yl- X.4 Racemicmixture Racemic mixture 3-bromo-propyl- X.5 Racemic mixture Racemicmixture 2,2,2-trifluoro-ethyl- X.6 Racemic mixture Racemic mixture3,3,3-trifluoro-propyl- X.7 Racemic mixture Racemic mixture cyclobutyl-X.8 Racemic mixture Racemic mixture methyl X.9 Racemic mixture Racemicmixture propyl X.10 Racemic mixture Racemic mixture 2,2-difluoro-ethyl-X.11 Racemic mixture Racemic mixture 2-fluoro-ethyl- X.12 S Racemicmixture ethyl- X.13 S Racemic mixture butyl- X.14 S Racemic mixturebut-2-yl- X.15 S Racemic mixture 3-bromo-propyl- X.16 S Racemic mixture2,2,2-trifluoro-ethyl- X.17 S Racemic mixture 3,3,3-trifluoro-propyl-X.18 S Racemic mixture cyclobutyl- X.19 S Racemic mixture methyl X.20 SRacemic mixture propyl X.21 S Racemic mixture 2,2-difluoro-ethyl- X.22 SRacemic mixture 2-fluoro-ethyl- X.23 Racemic mixture Racemic mixtureisopropyl X.24 Racemic mixture Racemic mixture cyclopropyl X.25 SRacemic mixture isopropyl X.26 S Racemic mixture cyclopropyl X.27Racemic mixture S ethyl- X.28 Racemic mixture S butyl- X.29 Racemicmixture S but-2-yl- X.30 Racemic mixture S 3-bromo-propyl- X.31 Racemicmixture S 2,2,2-trifluoro-ethyl- X.32 Racemic mixture S3,3,3-trifluoro-propyl- X.33 Racemic mixture S cyclobutyl- X.34 Racemicmixture S methyl X.35 Racemic mixture S propyl X.36 Racemic mixture S2,2-difluoro-ethyl- X.37 Racemic mixture S 2-fluoro-ethyl- X.38 S Sethyl- X.39 S S butyl- X.40 S S but-2-yl- X.41 S S 3-bromo-propyl- X.42S S 2,2,2-trifluoro-ethyl- X.43 S S 3,3,3-trifluoro-propyl- X.44 S Scyclobutyl- X.45 S S methyl X.46 S S propyl X.47 S S 2,2-difluoro-ethyl-X.48 S S 2-fluoro-ethyl- X.49 Racemic mixture S isopropyl X.50 Racemicmixture S cyclopropyl X.51 S S isopropyl X.52 S S cyclopropyl X.53Racemic mixture R ethyl- X.54 Racemic mixture R butyl- X.55 Racemicmixture R but-2-yl- X.56 Racemic mixture R 3-bromo-propyl- X.57 Racemicmixture R 2,2,2-trifluoro-ethyl- X.58 Racemic mixture R3,3,3-trifluoro-propyl- X.59 Racemic mixture R cyclobutyl- X.60 Racemicmixture R methyl X.61 Racemic mixture R propyl X.62 Racemic mixture R2,2-difluoro-ethyl- X.63 Racemic mixture R 2-fluoro-ethyl- X.64 S Rethyl- X.65 S R butyl- X.66 S R but-2-yl- X.67 S R 3-bromo-propyl- X.68S R 2,2,2-trifluoro-ethyl- X.69 S R 3,3,3-trifluoro-propyl- X.70 S Rcyclobutyl- X.71 S R methyl X.72 S R propyl X.73 S R 2,2-difluoro-ethyl-X.74 S R 2-fluoro-ethyl- X.75 Racemic mixture R isopropyl X.76 Racemicmixture R cyclopropyl X.77 S R isopropyl X.78 S R cyclopropyl

The compounds of the invention may be made by a variety of methods asshown in Schemes 1 to 3.

-   1) Compounds of formula (I), can be prepared by reacting a compound    of formula (II) wherein R is OH, C₁-C₆alkoxy or Cl, F or Br, with an    amine of formula (III) as shown in Scheme 1. When R is OH such    reactions are usually carried out in the presence of a coupling    reagent, such as N,N′-dicyclohexylcarbodiimide (“DCC”),    1-ethyl-3-(3-dimethylamino-propyl)carbodiimide hydrochloride (“EDC”)    or bis(2-oxo-3-oxazolidinyl)phosphonic chloride (“BOP-Cl”), in the    presence of a base, and optionally in the presence of a nucleophilic    catalyst, such as hydroxybenzotriazole (“HOBT”). When R is Cl, such    reactions are usually carried out in the presence of a base, and    optionally in the presence of a nucleophilic catalyst.    Alternatively, it is possible to conduct the reaction in a biphasic    system comprising an organic solvent, preferably ethyl acetate, and    an aqueous solvent, preferably a solution of sodium hydrogen    carbonate. When R is C₁-C₆alkoxy it is sometimes possible to convert    the ester directly to the amide by heating the ester and amine    together in a thermal process. Suitable bases include pyridine,    triethylamine, 4-(dimethylamino)-pyridine (“DMAP”) or    diisopropylethylamine (Hunig’s base). Preferred solvents are    N,Ndimethylacetamide, tetrahydrofuran, dioxane, 1,2-dimethoxyethane,    ethyl acetate and toluene. The reaction is carried out at a    temperature of from 0° C. to 100° C., preferably from 15° C. to 30°    C., in particular at ambient temperature. Amines of formula (III)    are either known in the literature or can be prepared using methods    known to a person skilled in the art.-   2) Acid halides of formula (II), wherein R is Cl, F or Br, may be    made from carboxylic acids of formula (II), wherein R is OH, under    standard conditions, as described for example in WO 2009/080250.-   3) Carboxylic acids of formula (II), wherein R is OH, may be formed    from esters of formula (II), wherein R is C₁-C₆alkoxy as described    for example in WO 2009/080250.-   4) Compounds of formula (I) can be prepared by reacting a compound    of formula (IV) wherein X^(B) is a leaving group, for example a    halogen, such as bromo, with carbon monoxide and an amine of formula    (III), in the presence of a catalyst, such as palladium(II) acetate    or bis-(triphenylphosphine)palladium(II) dichloride, optionally in    the presence of a ligand, such as triphenylphosphine, and a base,    such as sodium carbonate, pyridine, triethylamine,    4-(dimethylamino)-pyridine (“DMAP”) or diisopropylethylamine    (Hunig’s base), in a solvent, such as water, N,N-dimethylformamide    or tetrahydrofuran. The reaction is carried out at a temperature of    from 50° C. to 200° C., preferably from 100° C. to 150° C. The    reaction is carried out at a pressure of from 50 to 200 bar,    preferably from 100 to 150 bar.-   5) Compounds of formula (IV) wherein X^(B) is a leaving group, for    example a halogen, such as bromo, can be made by various methods,    for example as described in WO 2009/080250.

-   6) Alternatively, compounds of formula (I), can be prepared by    various methods from an intermediate of formula (V) as shown in    Scheme 2 wherein X^(B) is a leaving group, for example a halogen,    such as bromo, or X^(B) is cyano, formyl or acetyl according to    similar methods to those described in WO09080250. An intermediate of    formula (V) can be prepared for example from an intermediate of    formula (VI) as described in the same reference.

-   7) Alternatively, compounds of formula (I) can be prepared by    various methods from an intermediate of formula (VII) as shown in    Scheme 3 wherein X^(C) is X^(C)-1 or X^(C)-2

according to similar methods to those described in WO 2009/080250.

-   8) Compounds of formula (VII) wherein X^(C) is X^(C) is X^(C)-1 or    X^(C)-2 can be prepared from a compound of formula (Va) from a    compound of formula (VII) wherein X^(C) is CH₂-halogen using similar    methods to those described in WO 2009/080250.-   9) Compounds of formula (VII) wherein X^(C) is CH₂-halogen, such as    bromo or chloro, can be prepared by reacting a methyl ketone of    formula (Va) with a halogenating agent, such as bromine or chlorine,    in a solvent, such as acetic acid, at a temperature of from 0° C. to    50° C., preferably from ambient temperature to 40° C.

Other methods for the preparation of compounds of formula I aredescribed in PCT/EP2010/068605, which is incorporated herein byreference.

The methods and uses of the invention are preferably for controllingand/or preventing infestation of the soybean crop by stink bugs,including stink bugs that are resistant to other insecticides, e.g.pyrethroid insecticides. Stinkbugs that are “resistant” to a particularinsecticide refers e.g. to strains of stinkbugs that are less sensitiveto that insecticide compared to the expected sensitivity of the samespecies of stinkbug. The expected sensitivity can be measured using e.g.a strain that has not previously been exposed to the insecticide.

Application is of the compounds of the invention is preferably to a cropof soybean plants, the locus thereof or propagation material thereof.Preferably application is to a crop of soybean plants or the locusthereof, more preferably to a crop of soybean plants. Application may bebefore infestation or when the pest is present. Application of thecompounds of the invention can be performed according to any of theusual modes of application, e.g. foliar, drench, soil, in furrow etc.However, control of stinkbugs is usually achieved by foliar application,which is the preferred mode of application according to the invention.

The compounds of the invention may be applied in combination with anattractant. An attractant is a chemical that causes the insect tomigrate towards the location of application. For control of stinkbugs itcan be advantageous to apply the compounds of the invention with anattractant, particularly when the application is foliar. Stinkbugs areoften located near to the ground, and application of an attractant mayencourage migration up the plant towards the active ingredient. Suitableattractants include glucose, sacchrose, salt, glutamate (e.g.Aji-no-moto™), citric acid (e.g. Orobor™), soybean oil, peanut oil andsoybean milk. Glutamate and citric acid are of particular interest, withcitric acid being preferred.

An attractant may be premixed with the compound of the invention priorto application, e.g. as a readymix or tankmix, or by simultaneousapplication or sequential application to the plant. Suitable rates ofattractants are for example 0.02 kg/ha-3 kg/ha.

The compounds of the invention are preferably used for pest control onsoybean at 1:500 g/ha, preferably 10-70 g/ha.

The compounds of the invention are suitable for use on any soybeanplant, including those that have been genetically modified to beresistant to active ingredients such as herbicides, or to producebiologically active compounds that control infestation by plant pests.

In a further preferred embodiment, transgenic plants and plant cultivarsobtained by genetic engineering methods, if appropriate in combinationwith conventional methods (Genetically Modified Organisms), and partsthereof, are treated. Particularly preferably, plants of the plantcultivars which are in each case commercially available or in use aretreated according to the invention. Plant cultivars are understood asmeaning plants having novel properties (“traits”) which have beenobtained by conventional breeding, by mutagenesis or by recombinant DNAtechniques.

These can be cultivars, bio- or genotypes. Depending on the plantspecies or plant cultivars, their location and growth conditions (soils,climate, vegetation period, diet), the treatment according to theinvention may also result in superadditive “synergistic”) effects.

Thus, for example, reduced application rates and/or a widening of theactivity spectrum and/or an increase in the activity of the substancesand compositions which can be used according to the invention, betterplant growth, increased tolerance to high or low temperatures, increasedtolerance to drought or to water or soil salt content, increasedflowering performance, easier harvesting, accelerated maturation, higherharvest yields, higher quality and/or a higher nutritional value of theharvested products, better storage stability and/or processability ofthe harvested products are possible, which exceed the effects which wereactually to be expected.

The preferred transgenic plants or plant cultivars (obtained by geneticengineering) which are to be treated according to the invention includeall plants which, by virtue of the genetic modification, receivedgenetic material which imparts particularly advantageous, useful traitsto these plants. Examples of such traits are better plant growth,increased tolerance to high or low temperatures, increased tolerance todrought or to water or soil salt content, increased floweringperformance, easier harvesting, accelerated maturation, higher harvestyields, higher quality and/or a higher nutritional value of theharvested products, better storage stability and/or processability ofthe harvested products.

Further and particularly emphasized examples of such traits are a betterdefence of the plants against animal and microbial pests, such asagainst insects, mites, phytopathogenic fungi, bacteria and/or viruses,and also increased tolerance of the plants to certain herbicidallyactive compounds.

Traits that are emphasized in particular are the increased defence ofthe plants against insects, arachnids, nematodes and slugs and snails byvirtue of toxins formed in the plants, in particular those formed in theplants by the genetic material from Bacillus thuringiensis (for exampleby the genes CrylA(a), CrylA(b), CrylA(c), CryllA, CrylllA, CryIIIB2,Cry9c, Cry2Ab, Cry3Bb and CrylF and also combinations thereof) (referredto herein as “Bt plants”). Traits that are also particularly emphasizedare the increased defence of the plants against fungi, bacteria andviruses by systemic acquired resistance (SAR), systemin, phytoalexins,elicitors and resistance genes and correspondingly expressed proteinsand toxins.

Traits that are furthermore particularly emphasized are the increasedtolerance of the plants to certain herbicidally active compounds, forexample imidazolinones, sulphonylureas, glyphosate or phosphinotricin(for example the “PAT” gene). The genes which impart the desired traitsin question can also be present in combination with one another in thetransgenic plants.

Examples of “Bt plants” are soya bean varieties which are sold under thetrade names YIELD GARD(®)

Examples of herbicide-tolerant plants which may be mentioned are soybeanvarieties which are sold under the trade names Roundup Ready®(toleranceto glyphosate), Liberty Link® (tolerance to phosphinotricin),IMI®(tolerance to imidazolinones) and STS® (tolerance tosulphonylureas).

Herbicide-resistant plants (plants bred in a conventional manner forherbicide tolerance) which may be mentioned include the varieties soldunder the name Clearfield® (for example maize).

Of particular interest are soybean plants carrying trains conferringresistance to 2.4D (e.g. Enlist®), glyphosate (e.g. Roundup Ready®,Roundup Ready 2 Yield®), sulfonylurea (e.g. STS®), glufosinate (e.g.Liberty Link®, Ignite®), Dicamba (Monsanto) HPPD tolerance (e.g.isoxaflutole herbicide) (Bayer CropScience, Syngenta). Double or triplestack in soybean plants of any of the traits described here are also ofinterest, including glyphosate and sulfonyl-urea tolerance (e.g. OptimumGAT®, plants stacked with STS® and Roundup Ready® or Roundup Ready 2Yield®), dicamba and glyphosate tolerance (Monsanto). Soybean CystNematode resistance soybean (SCN® - Syngenta) and soybean with Aphidresistant trait (AMT® - Syngneta) are also of interest.

These statements also apply to plant cultivars having these genetictraits or genetic traits still to be developed, which plant cultivarswill be developed and/or marketed in the future.

The compounds of the invention may be used on soybean to control, forexample, Elasmopalpus lignosellus, Diloboderus abderus, Diabroticaspeciosa, Sternechus subsignatus, Formicidae, Agrotis ypsilon, Julusssp., Anticarsia gemmatalis, Megascelis ssp., Procornitermes ssp.,Gryllotalpidae, Nezara viridula, Piezodorus spp., Acrostemum spp.,Neomegalotomus spp., Cerotoma trifurcata, Popillia japonica, Edessaspp., Liogenys fuscus, Euchistus heros, stalk borer, Scaptocoriscastanea, phyllophaga spp., Pseudoplusia includens, Spodoptera spp.,Bemisia tabaci, Agriotes spp., preferably Diloboderus abderus,Diabrotica speciosa, Nezara viridula, Piezodorus spp., Acrosternum spp.,Cerotoma trifurcata, Popillia japonica, Euchistus heros, phyllophagaspp., Agriotes spp..

The compounds of the invention are preferably used on soybean to controlstinkbugs, e.g. Nezara spp. (e.g. Nezara viridula, Nezara antennata,Nezara hilare), Piezodorus spp. (e.g. Piezodorus guildinii), Acrosternumspp. Euchistus spp. (e.g. Euchistus heros, Euschistus servus),Halyomorpha halys, Plautia crossota, Riptortus clavatus, Rhopalusmsculatus, Antestiopsis orbitalus, Dichelops spp. (e.g. Dichelopsfurcatus, Dichelops melacanthus), Eurygaster spp. (e.g. Eurygasterintergriceps, Eurygaster maura), Oebalus spp. (e.g. Oebalus mexicana,Oebalus poecilus, Oebalus pugnase, Scotinophara spp. (e.g. Scotinopharalurida, Scotinophara coarctata). Preferred targets include Antestiopsisorbitalus, Dichelops furcatus, Dichelops melacanthus, Euchistus heros,Euschistus servus, Nezara viridula, Nezara hilare, Piezodorus guildinii,Halyomorpha halys. In one embodiment the stinkbug target is Nezaraviridula, Piezodorus spp., Acrosternum spp, Euchistus heros. Thecompounds of the invention are particularly effective against Euschistusand in particular Euchistus heros. Euschistus and in particularEuchistus heros are the preferred targets.

In order to apply a compounds of the invention as an insecticide,acaricide, nematicide or molluscicide to a pest, a locus of pest, or toa plant susceptible to attack by a pest, compounds of the invention isusually formulated into a composition which includes, in addition to thecompound of the invention, a suitable inert diluent or carrier and,optionally, a surface active agent (SFA). SFAs are chemicals which areable to modify the properties of an interface (for example,liquid/solid, liquid/air or liquid/liquid interfaces) by lowering theinterfacial tension and thereby leading to changes in other properties(for example dispersion, emulsification and wetting). It is preferredthat all compositions (both solid and liquid formulations) comprise, byweight, 0.0001 to 95%, more preferably 1 to 85%, for example 5 to 60%,of a compound of the invention. The composition is generally used forthe control of pests such that a compound of the invention is applied ata rate of from 0.1 g to 10 kg per hectare, preferably from 1 g to 6 kgper hectare, more preferably from 1 g to 1 kg per hectare.

When used in a seed dressing, a compound of the invention is used at arate of 0.0001 g to 10 g (for example 0.001 g or 0.05 g), preferably0.005 g to 10 g, more preferably 0.005 g to 4 g, per kilogram of seed.

Compositions comprising a compound of the invention can be chosen from anumber of formulation types, including dustable powders (DP), solublepowders (SP), water soluble granules (SG), water dispersible granules(WG), wettable powders (WP), granules (GR) (slow or fast release),soluble concentrates (SL), oil miscible liquids (OL), ultra low volumeliquids (UL), emulsifiable concentrates (EC), dispersible concentrates(DC), emulsions (both oil in water (EW) and water in oil (EO)),micro-emulsions (ME), suspension concentrates (SC), aerosols,fogging/smoke formulations, capsule suspensions (CS) and seed treatmentformulations. The formulation type chosen in any instance will dependupon the particular purpose envisaged and the physical, chemical andbiological properties of the compound of the invention.

Dustable powders (DP) may be prepared by mixing a compound of theinvention with one or more solid diluents (for example natural clays,kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr,chalk, diatomaceous earths, calcium phosphates, calcium and magnesiumcarbonates, sulfur, lime, flours, talc and other organic and inorganicsolid carriers) and mechanically grinding the mixture to a fine powder.

Soluble powders (SP) may be prepared by mixing a compound of theinvention with one or more water-soluble inorganic salts (such as sodiumbicarbonate, sodium carbonate or magnesium sulfate) or one or morewater-soluble organic solids (such as a polysaccharide) and, optionally,one or more wetting agents, one or more dispersing agents or a mixtureof said agents to improve water dispersibility/solubility. The mixtureis then ground to a fine powder. Similar compositions may also begranulated to form water soluble granules (SG).

Wettable powders (WP) may be prepared by mixing a compound of theinvention with one or more solid diluents or carriers, one or morewetting agents and, preferably, one or more dispersing agents and,optionally, one or more suspending agents to facilitate the dispersionin liquids. The mixture is then ground to a fine powder. Similarcompositions may also be granulated to form water dispersible granules(WG).

Granules (GR) may be formed either by granulating a mixture of acompound of the invention and one or more powdered solid diluents orcarriers, or from pre-formed blank granules by absorbing a compound ofthe invention (or a solution thereof, in a suitable agent) in a porousgranular material (such as pumice, attapulgite clays, fuller’s earth,kieselguhr, diatomaceous earths or ground corn cobs) or by adsorbing acompound of the invention (or a solution thereof, in a suitable agent)on to a hard core material (such as sands, silicates, mineralcarbonates, sulfates or phosphates) and drying if necessary. Agentswhich are commonly used to aid absorption or adsorption include solvents(such as aliphatic and aromatic petroleum solvents, alcohols, ethers,ketones and esters) and sticking agents (such as polyvinyl acetates,polyvinyl alcohols, dextrins, sugars and vegetable oils). One or moreother additives may also be included in granules (for example anemulsifying agent, wetting agent or dispersing agent).

Dispersible Concentrates (DC) may be prepared by dissolving a compoundof the invention in water or an organic solvent, such as a ketone,alcohol or glycol ether. These solutions may contain a surface activeagent (for example to improve water dilution or prevent crystallizationin a spray tank).

Emulsifiable concentrates (EC) or oil-in-water emulsions (EW) may beprepared by dissolving a compound of the invention in an organic solvent(optionally containing one or more wetting agents, one or moreemulsifying agents or a mixture of said agents). Suitable organicsolvents for use in ECs include aromatic hydrocarbons (such asalkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100,SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark),ketones (such as cyclohexanone or methylcyclohexanone) and alcohols(such as benzyl alcohol, furfuryl alcohol or butanol),N-alkylpyrrolidones (such as N-methylpyrrolidone or N-octylpyrrolidone),dimethyl amides of fatty acids (such as C₈-C₁₀ fatty acid dimethylamide)and chlorinated hydrocarbons. An EC product may spontaneously emulsifyon addition to water, to produce an emulsion with sufficient stabilityto allow spray application through appropriate equipment. Preparation ofan EW involves obtaining a compound of the invention either as a liquid(if it is not a liquid at room temperature, it may be melted at areasonable temperature, typically below 70° C.) or in solution (bydissolving it in an appropriate solvent) and then emulsifiying theresultant liquid or solution into water containing one or more SFAs,under high shear, to produce an emulsion. Suitable solvents for use inEWs include vegetable oils, chlorinated hydrocarbons (such aschlorobenzenes), aromatic solvents (such as alkylbenzenes oralkylnaphthalenes) and other appropriate organic solvents which have alow solubility in water.

Microemulsions (ME) may be prepared by mixing water with a blend of oneor more solvents with one or more SFAs, to produce spontaneously athermodynamically stable isotropic liquid formulation. A compound of theinvention is present initially in either the water or the solvent/SFAblend. Suitable solvents for use in MEs include those hereinbeforedescribed for use in ECs or in EWs. An ME may be either an oil-in-wateror a water-in-oil system (which system is present may be determined byconductivity measurements) and may be suitable for mixing water-solubleand oil-soluble pesticides in the same formulation. An ME is suitablefor dilution into water, either remaining as a microemulsion or forminga conventional oil-in-water emulsion.

Suspension concentrates (SC) may comprise aqueous or non-aqueoussuspensions of finely divided insoluble solid particles of a compound ofthe invention. SCs may be prepared by ball or bead milling the solidcompound of the invention in a suitable medium, optionally with one ormore dispersing agents, to produce a fine particle suspension of thecompound. One or more wetting agents may be included in the compositionand a suspending agent may be included to reduce the rate at which theparticles settle. Alternatively, a compound of the invention may be drymilled and added to water, containing agents hereinbefore described, toproduce the desired end product.

Aerosol formulations comprise a compound of the invention and a suitablepropellant (for example n-butane). A compound of the invention may alsobe dissolved or dispersed in a suitable medium (for example water or awater miscible liquid, such as n-propanol) to provide compositions foruse in non-pressurized, hand-actuated spray pumps.

A compound of the invention may be mixed in the dry state with apyrotechnic mixture to form a composition suitable for generating, in anenclosed space, a smoke containing the compound.

Capsule suspensions (CS) may be prepared in a manner similar to thepreparation of EW formulations but with an additional polymerizationstage such that an aqueous dispersion of oil droplets is obtained, inwhich each oil droplet is encapsulated by a polymeric shell and containsa compound of the invention and, optionally, a carrier or diluenttherefor. The polymeric shell may be produced by either an interfacialpolycondensation reaction or by a coacervation procedure. Thecompositions may provide for controlled release of the compound of theinvention and they may be used for seed treatment. A compound of theinvention may also be formulated in a biodegradable polymeric matrix toprovide a slow, controlled release of the compound.

A composition may include one or more additives to improve thebiological performance of the composition (for example by improvingwetting, retention or distribution on surfaces; resistance to rain ontreated surfaces; or uptake or mobility of a compound of the invention).Such additives include surface active agents, spray additives based onoils, for example certain mineral oils or natural plant oils (such assoy bean and rape seed oil), and blends of these with otherbio-enhancing adjuvants (ingredients which may aid or modify the actionof a compound of the invention).

A compound of the invention may also be formulated for use as a seedtreatment, for example as a powder composition, including a powder fordry seed treatment (DS), a water soluble powder (SS) or a waterdispersible powder for slurry treatment (WS), or as a liquidcomposition, including a flowable concentrate (FS), a solution (LS) or acapsule suspension (CS). The preparations of DS, SS, WS, FS and LScompositions are very similar to those of, respectively, DP, SP, WP, SCand DC compositions described above. Compositions for treating seed mayinclude an agent for assisting the adhesion of the composition to theseed (for example a mineral oil or a film-forming barrier).

Wetting agents, dispersing agents and emulsifying agents may be surfaceSFAs of the cationic, anionic, amphoteric or non-ionic type.

Suitable SFAs of the cationic type include quaternary ammonium compounds(for example cetyltrimethyl ammonium bromide), imidazolines and aminesalts.

Suitable anionic SFAs include alkali metals salts of fatty acids, saltsof aliphatic monoesters of sulfuric acid (for example sodium laurylsulfate), salts of sulfonated aromatic compounds (for example sodiumdodecylbenzenesulfonate, calcium dodecylbenzenesulfonate,butylnaphthalene sulfonate and mixtures of sodium di-isopropyl- andtri-isopropyl-naphthalene sulfonates), ether sulfates, alcohol ethersulfates (for example sodium laureth-3-sulfate), ether carboxylates (forexample sodium laureth-3-carboxylate), phosphate esters (products fromthe reaction between one or more fatty alcohols and phosphoric acid(predominately mono-esters) or phosphorus pentoxide (predominatelydi-esters), for example the reaction between lauryl alcohol andtetraphosphoric acid; additionally these products may be ethoxylated),sulfosuccinamates, paraffin or olefine sulfonates, taurates andlignosulfonates.

Suitable SFAs of the amphoteric type include betaines, propionates andglycinates.

Suitable SFAs of the non-ionic type include condensation products ofalkylene oxides, such as ethylene oxide, propylene oxide, butylene oxideor mixtures thereof, with fatty alcohols (such as oleyl alcohol or cetylalcohol) or with alkylphenols (such as octylphenol, nonylphenol oroctylcresol); partial esters derived from long chain fatty acids orhexitol anhydrides; condensation products of said partial esters withethylene oxide; block polymers (comprising ethylene oxide and propyleneoxide); alkanolamides; simple esters (for example fatty acidpolyethylene glycol esters); amine oxides (for example lauryl dimethylamine oxide); and lecithins.

Suitable suspending agents include hydrophilic colloids (such aspolysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose)and swelling clays (such as bentonite or attapulgite).

A compound of the invention may be applied by any of the known means ofapplying pesticidal compounds. For example, it may be applied,formulated or unformulated, to the pests or to a locus of the pests(such as a habitat of the pests, or a growing plant liable toinfestation by the pests) or to any part of the plant, including thefoliage, stems, branches or roots, to the seed before it is planted orto other media in which plants are growing or are to be planted (such assoil surrounding the roots, the soil generally, paddy water orhydroponic culture systems), directly or it may be sprayed on, dustedon, applied by dipping, applied as a cream or paste formulation, appliedas a vapor or applied through distribution or incorporation of acomposition (such as a granular composition or a composition packed in awater-soluble bag) in soil or an aqueous environment.

A compound of the invention may also be injected into plants or sprayedonto vegetation using electrodynamic spraying techniques or other lowvolume methods, or applied by land or aerial irrigation systems.

Compositions for use as aqueous preparations (aqueous solutions ordispersions) are generally supplied in the form of a concentratecontaining a high proportion of the active ingredient, the concentratebeing added to water before use. These concentrates, which may includeDCs, SCs, ECs, EWs, MEs, SGs, SPs, WPs, WGs and CSs, are often requiredto withstand storage for prolonged periods and, after such storage, tobe capable of addition to water to form aqueous preparations whichremain homogeneous for a sufficient time to enable them to be applied byconventional spray equipment. Such aqueous preparations may containvarying amounts of a compound of the invention (for example 0.0001 to10%, by weight) depending upon the purpose for which they are to beused.

A compound of the invention may be used in mixtures with fertilizers(for example nitrogen-, potassium- or phosphorus-containingfertilizers). Suitable formulation types include granules of fertilizer.The mixtures preferably contain up to 25% by weight of the compound ofthe invention.

The invention therefore also provides a fertilizer compositioncomprising a fertilizer and a compound of the invention.

The compositions of this invention may contain other compounds havingbiological activity, for example micronutrients or compounds havingfungicidal activity or which possess plant growth regulating,herbicidal, insecticidal, nematicidal or acaricidal activity.

The compound of the invention may be the sole active ingredient of thecomposition or it may be admixed with one or more additional activeingredients such as a pesticide, fungicide, synergist, herbicide orplant growth regulator where appropriate. An additional activeingredient may: provide a composition having a broader spectrum ofactivity or increased persistence at a locus; synergize the activity orcomplement the activity (for example by increasing the speed of effector overcoming repellency) of the compound of the invention; or help toovercome or prevent the development of resistance to individualcomponents. The particular additional active ingredient will depend uponthe intended utility of the composition. Examples of suitable pesticidesinclude the following:

-   a) Pyrethroids, such as permethrin, cypermethrin, fenvalerate,    esfenvalerate, deltamethrin, cyhalothrin (in particular    lambda-cyhalothrin and gamma cyhalothrin), bifenthrin,    fenpropathrin, cyfluthrin, tefluthrin, fish safe pyrethroids (for    example ethofenprox), natural pyrethrin, tetramethrin,    S-bioallethrin, fenfluthrin, prallethrin, acrinathirin, etofenprox    or    5-benzyl-3-furyhnethyl-(E)-(1R,3S)-2,2-dimethyl-3-(2-oxothiolan-3-ylidenemethyl)cyclopropane    carboxylate;-   b) Organophosphates, such as profenofos, sulprofos, acephate, methyl    parathion, azinphos-methyl, demeton-s-methyl, heptenophos,    thiometon, fenamiphos, monocrotophos, profenofos, triazophos,    methamidophos, dimethoate, phosphamidon, malathion, chlorpyrifos,    phosalone, terbufos, fensulfothion, fonofos, phorate, phoxim,    pirimiphos-methyl, pirimiphos-ethyl, fenitrothion, fosthiazate or    diazinon;-   c) Carbamates (including aryl carbamates), such as pirimicarb,    triazamate, cloethocarb, carbofuran, furathiocarb, ethiofencarb,    aldicarb, thiofurox, carbosulfan, bendiocarb, fenobucarb, propoxur,    methomyl or oxamyl;-   d) Benzoyl ureas, such as diflubenzuron, triflumuron, hexaflumuron,    flufenoxuron, diafenthiuron, lufeneron, novaluron, noviflunuron or    chlorfluazuron;-   e) Organic tin compounds, such as cyhexatin, fenbutatin oxide or    azocyclotin;-   f) Pyrazoles, such as tebufenpyrad, tolfenpyrad, ethiprole,    pyriprole, fipronil, and fenpyroximate;-   g) Macrolides, such as avermectins or milbemycins, for example    abamectin, emamectin benzoate, ivermectin, milbemycin, spinosad,    azadirachtin, milbemectin, lepimectin or spinetoram;-   h) Hormones or pheromones;-   i) Organochlorine compounds, such as endosulfan (in particular    alpha-endosulfan), benzene hexachloride, DDT, chlordane or dieldrin;-   j) Amidines, such as chlordimeform or amitraz;-   k) Fumigant agents, such as chloropicrin, dichloropropane, methyl    bromide or metam;-   1) Neonicotinoid compounds, such as imidacloprid, thiacloprid,    acetamiprid, nitenpyram, dinotefuran, thiamethoxam, clothianidin, or    nithiazine;-   m) Diacylhydrazines, such as tebufenozide, chromafenozide or    methoxyfenozide;-   n) Diphenyl ethers, such as diofenolan or pyriproxifen;-   o) Ureas such as Indoxacarb or metaflumizone;-   p) Ketoenols, such as Spirotetramat, spirodiclofen or spiromesifen;-   q) Diamides, such as flubendiamide, chlorantraniliprole (Rynaxypyr®)    or cyantraniliprole;-   r) Essential oils such as Bugoil® - (PlantImpact); or-   s) a comopund selected from buprofezine, flonicamid, acequinocyl,    bifenazate, cyenopyrafen, cyflumetofen, etoxazole, flometoquin,    fluacrypyrim, fluensulfone, flufenerim, flupyradifuone, harpin,    iodomethane, dodecadienol, pyridaben, pyridalyl, pyrimidifen,    flupyradifurone,    4-[(6-Chloro-pyridin-3-ylmethyl)-(2,2-difluoro-ethyl)-amino]-5H-furan-2-one    (DE 102006015467), CAS: 915972-17-7 (WO 2006129714; WO 2011/147953;    WO 2011/147952), CAS: 26914-55-8 (WO 2007/020986), chlorfenapyr,    pymetrozine, sulfoxaflor and pyrifluginazon.

In addition to the major chemical classes of pesticide listed above,other pesticides having particular targets may be employed in thecomposition, if appropriate for the intended utility of the composition.For instance, selective insecticides for particular crops, for examplestemborer specific insecticides (such as cartap) or hopper specificinsecticides (such as buprofezin) for use in rice may be employed.Alternatively insecticides or acaricides specific for particular insectspecies/stages may also be included in the compositions (for exampleacaricidal ovo-larvicides, such as clofentezine, flubenzimine,hexythiazox or tetradifon; acaricidal motilicides, such as dicofol orpropargite; acaricides, such as bromopropylate or chlorobenzilate; orgrowth regulators, such as hydramethylnon, cyromazine, methoprene,chlorfluazuron or diflubenzuron).

Examples of fungicidal compounds which may be included in thecomposition of the invention are(E)-N-methyl-2-[2-(2,5-dimethylphenoxymethyl)phenyl]-2-methoxy-iminoacetamide(SSF-129),4-bromo-2-cyano-N,N-dimethyl-6-trifluoromethylbenzimidazole-1-sulfonamide,α-[N-(3-chloro-2,6--xylyl)-2-methoxyacetamido]-γ-butyrolactone,4-chloro-2-cyano-N,N-dimethyl-5-p-tolylimidazole-1-sulfonamide (IKF-916,cyamidazosulfamid),3-5-dichloro-N-(3-chloro-1-ethyl-1-methyl-2-oxopropyl)-4-methylbenzamide(RH-7281, zoxamide),N-allyl-4,5,-dimethyl-2-trimethylsilylthiophene-3-carboxamide(MON65500),N-(1-cyano-1,2-dimethylpropyl)-2-(2,4-dichlorophenoxy)propionamide(AC382042), N-(2-methoxy-5-pyridyl)-cyclopropane carboxamide,acibenzolar (CGA245704), alanycarb, aldimorph, anilazine, azaconazole,azoxystrobin, benalaxyl, benomyl, biloxazol, bitertanol, blasticidin S,bromuconazole, bupirimate, captafol, captan, carbendazim, carbendazimchlorhydrate, carboxin, carpropamid, carvone, CGA41396, CGA41397,chinomethionate, chlorothalonil, chlorozolinate, clozylacon, coppercontaining compounds such as copper oxychloride, copper oxyquinolate,copper sulfate, copper tallate and Bordeaux mixture, cymoxanil,cyproconazole, cyprodinil, debacarb, di-2-pyridyl disulfide1,1′-dioxide, dichlofluanid, diclomezine, dicloran, diethofencarb,difenoconazole, difenzoquat, diflumetorim, O,O-di-iso-propyl-S-benzylthiophosphate, dimefluazole, dimetconazole, dimethomorph, dimethirimol,diniconazole, dinocap, dithianon, dodecyl dimethyl ammonium chloride,dodemorph, dodine, doguadine, edifenphos, epoxiconazole, ethirimol,ethyl-(Z)-N-benzyl-N-([methyl(methyl-thioethylideneaminooxycarbonyl)amino]thio)-β-alaninate,etridiazole, famoxadone, fenamidone (RPA407213), fenarimol,fenbuconazole, fenfuram, fenhexamid (KBR2738), fenpiclonil, fenpropidin,fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzone,fluazinam, fludioxonil, flumetover, fluoroimide, fluquinconazole,flusilazole, flutolanil, flutriafol, folpet, fuberidazole, furalaxyl,furametpyr, guazatine, hexaconazole, hydroxyisoxazole, hymexazole,imazalil, imibenconazole, iminoctadine, iminoctadine triacetate,ipconazole, iprobenfos, iprodione, iprovalicarb (SZX0722), isopropanylbutyl carbamate, isoprothiolane, kasugamycin, kresoxim-methyl, LY186054,LY211795, LY248908, mancozeb, maneb, mefenoxam, mepanipyrim, mepronil,metalaxyl, metconazole, metiram, metiram-zinc, metominostrobin,myclobutanil, neoasozin, nickel dimethyldithiocarbamate,nitrothal-isopropyl, nuarimol, ofurace, organomercury compounds,oxadixyl, oxasulfuron, oxolinic acid, oxpoconazole, oxycarboxin,pefurazoate, penconazole, pencycuron, phenazin oxide, phosetyl-Al,phosphorus acids, phthalide, picoxystrobin (ZA1963), poly-oxin D,polyram, probenazole, prochloraz, procymidone, propamocarb,propiconazole, propineb, propionic acid, pyrazophos, pyrifenox,pyrimethanil, pyroquilon, pyroxyfur, pyrrolnitrin, quaternary ammoniumcompounds, quinomethionate, quinoxyfen, quintozene, sipconazole (F-155),sodium pentachlorophenate, spiroxamine, streptomycin, sulfur,tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole,thifluzamid, 2-(thiocyanomethylthio)benzothiazole, thiophanate-methyl,thiram, timibenconazole, tolclofos-methyl, tolylfluanid, triadimefon,triadimenol, triazbutil, triazoxide, tricyclazole, tridemorph,trifloxystrobin (CGA279202), triforine, triflumizole, triticonazole,validamycin A, vapam, vinclozolin, zineb, ziram;N-[9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide[1072957-71-1], 1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxylic acid(2-dichloromethylene-3-ethyl-1-methyl-indan-4-yl)-amide, and1-methyl-3-difluoromethyl-4H-pyrazole-4-carboxylic acid[2-(2,4-dichlorophenyl)-2-methoxy-1-methyl-ethyl]-amide.

Preferred additional pesticidally active ingredients are those selectedfrom neonicotinoids, pyrethroids, strobilurins, triazoles andcarboxamides (SDHI inhibitors). Pyrethroids are of interest of whichlambda-cyhalothrin is of particular interest. Combinations of compoundsof the invention and pyrethroids, in parrticular lambda-cyhalothrin,exhibit synergistic control of stinkbugs (according to the Colbyformula), in particular Euschistus, e.g. Euschistus heros.

In a further aspect of the invention there is provided a methodcomprising applying to a crop of soybean plants, the locus thereof, orpropagation material thereof, a combination of a compound a compound ofthe invention and lambda cyhalothrin in a synergistically effectiveamount, wherein the method is for control and/or prevention ofstinkbugs, preferably Euschistus, e.g. Euschistus heros.

The compounds of the invention may be mixed with soil, peat or otherrooting media for the protection of plants against seed-borne,soil-borne or foliar fungal diseases.

Examples of suitable synergists for use in the compositions includepiperonyl butoxide, sesamex, safroxan and dodecyl imidazole.

Suitable herbicides and plant-growth regulators for inclusion in thecompositions will depend upon the intended target and the effectrequired.

An example of a rice selective herbicide which may be included ispropanil. An example of a plant growth regulator for use in cotton isPIX™.

Some mixtures may comprise active ingredients which have significantlydifferent physical, chemical or biological properties such that they donot easily lend themselves to the same conventional formulation type. Inthese circumstances other formulation types may be prepared. Forexample, where one active ingredient is a water insoluble solid and theother a water insoluble liquid, it may nevertheless be possible todisperse each active ingredient in the same continuous aqueous phase bydispersing the solid active ingredient as a suspension (using apreparation analogous to that of an SC) but dispersing the liquid activeingredient as an emulsion (using a preparation analogous to that of anEW). The resultant composition is a suspoemulsion (SE) formulation.

Unless otherwise stated the weight ratio of the compound of I with anadditional active ingredient may generally be between 1000 : 1 and 1 :1000. In other embodiments that weight ratio of A to B may be between500 : 1 to 1 : 500, for example between 100 : 1 to 1 : 100, for examplebetween 1 : 50 to 50 : 1, for example 1 : 20 to 20 : 1, for example 1:10to 10:1, for example 1:5 to 5:1, for example 1:1.

Compositions of the invention include those prepared by premixing priorto application, e.g. as a readymix or tankmix, or by simultaneousapplication or sequential application to the plant.

The invention will now be illustrated by the following non-limitingExamples. All citations are incorporated by reference.

BIOLOGICAL EXAMPLES

TABLE A Table A provides compounds of formula (Ia) wherein X¹, R¹, R⁴and R⁵ have the definitions shown below

(Ia) X1 R1 R4 R5 Stereochemistry at ^(∗) Stereochemistry at ^(∗∗) A13,4,5-trichlorophenyl ethyl C1 H S R A2 3,5-dichlorophenyl ethyl Br H SR A3 3,4,5-trichlorophenyl ethyl Br H S R A4 3,5-dichlorophenyl ethylCF3 H S R A5 3,4,5-trichlorophenyl ethyl CF3 H S R A63-trifluoromethylphenyl ethyl CH3 H S R A7 3,4,5-trichlorophenyl ethylCF3 H S R A8 3,5-dichlorophenyl ethyl CF3 H S R A9 3,5-dichlorophenylethyl Br H S R A10 3-chloro,5-trifluoromethylphenyl ethyl CH═CH—CH═CH SR A11 3,5-dichloro-4-fluorophenyl ethyl Cl H S R A123,5-dichloro-4-fluorophenyl ethyl CH3 H S R A13 3,4,5-trichlorophenyl2,2,2-trifluoroethyl CH3 H S R A14 3,4,5-trichlorophenyl2,2,2-trifluoroethyl CH3 H S R/S A15 3,5-dichlorophenyl methyl CH3 H SR/S A16 3,5-dichlorophenyl 2,2,2-trifluoroethyl CH3 H S S A173,5-dichlorophenyl ethyl CH3 H S S A18 3,5-dichloro-4-fluorophenyl EthylCH3 H S R/S A19 3,5-dichlorophenyl 2,2-difluoroethyl CH3 H S R/S A203,5-dichlorophenyl 2,2,2-trifluoroethyl CH3 H S R/S A213,5-dichlorophenyl ethyl CH3 H S R/S A22 3-chloro-5-bromophenyl2,2,2-trifluoroethyl CH3 H R/S R A23 3-chloro-5-bromophenyl ethyl CH3 HR/S R A24 3-chloro-5-trifluoromethylphenyl ethyl CH3 H R/S R A253,5-dichlorophenyl 2,2-difluoroethyl CH3 H S R A263,5-trifluoromethyl-4-chlorophenyl ethyl CH3 H R/S R A273,5-dichlorophenyl 2,2,2-trifluoroethyl CH3 H S R A28 3,5-dichlorophenylethyl CH3 H S R R/S indicates a racemic mixture.

TABLE B Table B provides compounds of formula (Ia) wherein X¹, R¹, R⁴and R⁵ have the definitions shown below

(Ib) B1 3,5-dichlorophenyl ethyl CH3 H R/S R

Euschistus Heros (Neotropical Brown Stink Bug) (Contact/FeedingActivity)

2 week old soybean plants are sprayed in a turn table spray chamber withthe diluted spray solutions. After drying, 2 soybean seeds are added andplants are infested with 10 N-2 nymphs of the neotropical brown stinkbug Euschistus heros in plastic test boxes. Boxes are incubated in aclimate chamber at 25° C. and 60 % RH. Evaluation is done 5 days afterinfestation on mortality and growth effects.

The following compounds showed at least 80% control at 50 ppm:

-   A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14, A15,    A16, A17, A18, A19, A20, A21, A22, A23, A24, A25, A26, A27, A28, B1-   The compounds enriched for the R stereochemistry at ^(∗∗) gave    superior performance at low application rates.

Comparative Example

Compounds are tested according to the above method. The results showthat the compounds of the invention are significantly more activeagainst Euschistus heros than structurally similar compounds,particularly at low rates of application.

Compound of the invention

Reference compound Compound Test Application rate / ppm Control / %Compound of the invention Euschistus heros (Neotropical brown stink bug)12.5 100 3 85 0.8 15 Reference compound Euschistus heros (Neotropicalbrown stink bug) 12.5 90 3 35 0.8 0

The compound of the invention and reference compound are compounds B5and B4 respectively from WO 2011/067272.

REFERENCES

Corrêa-Perreira, B. S.; Panizzi, A. R., Percevejos da soja e seu manejo,Londrina: Embrapa-CNPSo, 1999, 45 (Circular Técnica, 24).

Galileo, M.H.M., Heinrichs E.A., Retenção foliar em plantas de soja(glycine max (1.) merrill) resultantes da ação de Piezodorus guildinii(Westwood, 1837) (Hemiptera pentatomidae), em diferentes níveis e épocasde infestação. An. Soc. Entomol. Brasil, 1978, 7, 85-98.

Panizzi, A. R., Slansky junior, F. Review of phytophagous pentatomids(Hemiptera pentatomidae) associated with soybean in the Americas,Florida Entomologist, Gainesville, 1985, 68(1), 184-214.

Schmidt, F. G. V., Pires, C. S. S., Sujii, E. R,., Borges, M,.,Pantaleão, D. C., Lacerda, A. L., Azevedo, C. R., Comportamento ecaptura das fêmeas de Euschistus heros em armadilhas iscadas comferomonio sexual., 2003, Comunicado Técnico 93. Brasilia, DF.

Sosa-Gomez, D.R., Silva, J. Da., Lopes, I. O. N., Corso, I., Almeida,A.M. R. Almeida, moraes, g. c.p.m.; baur, m. insecticide susceptibilityof Euschistus heros (Heteroptera pentatomidae) in Brazil, Journal ofEconomic Entomology, 2009, 102(3), 1209-1216.

Todd, J. W., Herzog, D. C., Sampling phytophagous pentatomidae onsoybean. in: Kogan, M., Herzog, D. C. (ed.). Sampling methods in soybeanentomology, New York: Springer, 1980, 438-478.

1. A method of controlling pests on soybean plants, comprising: applyingto a crop of soybean plants, the locus thereof, or propagation materialthereof, a compound of formula (Ia),

wherein X¹, R¹, R⁴, R⁵, ^(∗), and ^(∗∗), as defined as follows X1 R1 R4R5 Stereochemistry at * Stereo-chemistry at ** A123,5-dichloro-4-fluorophenyl ethyl CH3 H S R A20 3,5-dichlorophenyl2,2,2-trifluoropethyl CH3 H S R/S A28 3,5-dichlorophenyl ethyl CH3 H S R

wherein the soybean plants are Bt plants.
 2. The method of claim 1,wherein the compound is compound A12

.
 3. The method of claim 1, wherein the compound is compound

.
 4. The method of claim 3, wherein the compound is

.
 5. The method of claim 1, wherein the compound is compound A28

.
 6. The method of claim 1, wherein the Bt plants comprise at least onegene selected from CrylA(a), CrylA(b), CrylA(c), CryllA, CrylllA,CryIIIB2, Cry9c, Cry2Ab, Cry3Bb and CrylF.
 7. The method of claim 6,wherein the at least one gene includes CrylA(a).
 8. The method of claim6, wherein at least one gene includes CrylA(b).
 9. The method of claim6, wherein at least one gene includes CrylA(c).
 10. The method of claim6, wherein at least one gene includes CryllA.
 11. The method of claim 6,wherein at least one gene includes CrylllA.
 12. The method of claim 6,wherein at least one gene includes CryIIIB2.
 13. The method of claim 6,wherein at least one gene includes Cry9c.
 14. The method of claim 6,wherein at least one gene includes Cry2Ab.
 15. The method of claim 6,wherein at least one gene includes Cry3Bb.
 16. The method of claim 6,wherein at least one gene includes CrylF.
 17. The method of claim 1,wherein the pest is a stinkbug.
 18. The method of claim 17, wherein thepest is a stinkbug Euschistus heros.
 19. The method of claim 1, whereinthe compound is applied at a rate of 1 g to 1 kg per hectare.
 20. Themethod of claim 1, wherein the applying is to a propagation material.21. The method of claim 1, wherein the compound is part of a compositionselected from dustable powders (DP), soluble powders (SP), water solublegranules (SG), water dispersible granules (WG), wettable powders (WP),granules (GR) (slow or fast release), soluble concentrates (SL), oilmiscible liquids (OL), ultra low volume liquids (UL), emulsifiableconcentrates (EC), dispersible concentrates (DC), emulsions (both oil inwater (EW) and water in oil (EO)), micro-emulsions (ME), suspensionconcentrates (SC), aerosols, fogging/smoke formulations, capsulesuspensions (CS) and seed treatment formulations.
 22. The method ofclaim 1, wherein the applying of the compound is admixed with one ormore additional active ingredients.
 23. The method of claim 22, whereinthe one or more additional active ingredients include at least one of apyrethroids, an organophosphate, a carbamate, a benzoyl urea, an organictin compound, a pyrazoles, hormones or pheromones, an organochlorine, anamidine, a fumigant, a neonicotinoid, a diacylhydrazines, a diphenylethers, a urea, a ketoenol, a diamides, or an essential oil.